A method for killing insects and mites

ABSTRACT

A composition of matter is described herein which has insecticidal and miticidal activity and methods of use. The composition may be defined by the following generic formula   wherein R1 is lower alkyl having 1 to 4 carbon atoms, and R2 can be selected from alkylketoximino, piperidyl, cycloalkylketoximino, alkylaldoximino, alkylcarbamylalkoxy, hexamethyleneimino, alkyloxazolidine, and   wherein R3 and R4 can be the same or different and can be selected from hydrogen, alkyl having 1 to 15 carbon atoms, alkoxyalkyl, alkenyl, benzyl, cyanoalkyl, alkanol, phenyl, alkylphenyl, sulfonamidophenyl, thiazolinyl, alkoxycarbamyl, halobenzyl, furfuryl, provided that when R3 is hydrogen, R4 is other than hydrogen.

United States Patent [1 1 Baker A 11] 3,917,827 Nov. 4, 1975 A METHODFOR KILLING INSECTS AND MITES [75] Inventor: Don R. Baker, Orinda,Calif.

[73] Assignee: Staufler Chemical Company,

Westport, Conn.

22 Filed: May 6,1974

21 Appl. No.: 466,930

Related US. Application Data [62] Division of Ser. No. 304,871, Oct. 19,1972, Pat. No.

Primary ExaminerAlbert T. Meyers Assistant ExaminerDale R. Ore Attorney,Agent, or FirmDanie1 C. Block [57] ABSTRACT A composition of matter isdescribed herein which has insecticidal and miticidal activity andmethods of use. The composition may be defined by the following genericformula CH cH cf 2 014 cH,-cH,

wherein R is lower alkyl having 1 to 4 carbon atoms, and R can beselected from alkylketoximino, piperidyl, cycloalkylketoximino,alkylaldoximino, alkylcarbamylalkoxy, hexamethyleneimino,alkyloxazolidine, and

wherein R and R, can be the same or different and can be selected fromhydrogen, alkyl having 1 to 15 carbon atoms, alkoxyalkyl, alkenyl,benzyl, cyanoalkyl, alkanol, phenyl, alkylph'e'nyl, sulfonamidophenyl,thiazolinyl, alkoxycarbamyl, halobenzyl, furfuryl, provided that when Ris hydrogen, R is other than hydrogen.

26 Claims, No Drawings METHOD FOR KILLING INSECTS AND MITES BACKGROUNDOF THE INVENTION Specifically, the organotins described in US. Pat. Nos.1

3,264,l77, 3,591,614 and 3,591,615 are widely used. These compounds,however, suffer from considerable unstability due to the presence of anester linkage to the tin atom. Thus, these compounds are quitesusceptible to hydrolysis on use. Additionally, the organotin compoundsdescribed in US. Pat.- Nos. 3,321,361 and 3,321,365 are useful asinsecticides. However, these compounds are quite toxic to vegetation andthus have extremely limited use.

BRIEF DESCRIPTION OF THE INVENTION It has been discovered that certainorganotin compounds have relatively low phytotoxicity properties and arerelatively stable. These organotin compounds may be defined by thefollowing generic formula fin-cu, CH2 CH Ca -cu,

wherein R is lower alkyl having 1 to 4 carbon atoms, and R can beselected from alkylketoximino, piperidyl, cycloalkylketoximino,alkylaldoximino, alkylcarbamylalkoxy, hexamethyleneimino,alkyloxazolidine, and

DETAILED DESCRIPTION OF THEINVENTION In the practice of the presentinvention, the compounds of the present invention are manufactured byreacting an alkylthiophosphine sulfide with an appropriate amine in aneutral solvent to form an intermediate compound. The intermediatecompound is then reacted with an alkyl tin halide to form the endproduct. The halide moiety in the alkyl tin halide can be selected fromthe group consisting of chlorine, bromine and iodine. After thecompounds of the present invention are formed, they can be applied tothe habitat in an effective amount to control respective mites andinsects.

The following examples illustrate the merits of the present invention:

EXAMPLE 1 A mixture was formed containing 2.2 grams (0.009 mole) ofethylthiophosphine sulfide, 50 ml. of tetrahydrofuran, 2.8 grams (0.015mole) of dodecylamine and 7.0 ml. of triethylamine. This mixture wasallowed-to stand for 1 hour wherein 6.1 grams (0.015 mole) oftricyclohexyl tin chloride was added and the mixture was allowed tostand for 24 hours. Then, the mixture was heated to boiling for a fewminutes, then diluted with 100 ml. of chloroform, washed with -100 ml.of water and ml. of sodium bicarbonate solution,'dried over magnesiumsulfate and evaporated in vacuo to yield 6.5 grams of product.

EXAMPLE 2 I ll SnSP 3 Ni-lcmcinocrr,

A mixture was formed containing 2.2 grams (0.009 mole) ofethylthiophosphine sulfide, 50 ml. tetrahydrofuran, and 3.0 grams (0.04mole) of methoxyethylamine. The mixture was allowed to stand for l 7hour, wherein 6.1 grams (0.015 mole) of tricyclohexyl tin chloride wasadded. The mixture was allowed to stand for 24 hours. Then, the mixturewas heated to boiling for a few minutes, diluted with 100 ml. ofchloroform, washed with 100 ml. of water and a 50 ml. solution of sodiumbicarbonate, dried over magnesium sulfate and evaporated in vacuo toyield 6.5 grams of product, m.p.

A mixture was formed containing 2.2' grams (0.009 mole) ofethylthiophosphine sulfide, 50 ml. of ethyl ether and 4.1 ml. (0.04mole) of diethylamine. This mixture was allowed to stand for 1 hour.Then, 6.1 grams (0.015 mole) of tricyclohexyl tin chloride and 50 ml.tetrahydrofuran was added and the mixture was allowed to stand for 24hours. Then, the mixture was boiled for a few minutes, diluted with 50ml. of ethyl ether and then washed with ml. of water, 50 ml. of asaturated solution of sodium bicarbonate, dried over magnesium sulfateand evaporated in vacuo to yield 7.0 grams of Broduct.

EXAMPLE 4 A mixture was formed containing 2.2 grams (0.009 mole) ofethylthiophosphine sulfide, 50 ml. tetrahydrofuran, 1.70 grams (0.015mole) of cyclohexanoneoxime and 7.0 ml. of triethylamine. This mixturereacted exothermically with the addition of triethylamine. After 1 hour,6.0 grams (0.015 mole) of tricyclohexyl tin chloride was added andallowed to stand for 2 days. The mixture was diluted with 100 ml. ofchloroform. The mixture was then washed with 100 ml. of water, 50 ml. ofsaturated sodium bicarbonate solution, dried over magnesium sulfate andevaporated in vacuo to yield an oil that was triturated with methanol toyield 7.2 g. of crystals, m.p. 7679C.

EXAMPLE c i-i, O Q 3 \NH .The procedure of Example 4 was repeated in itsentirety except 1.8 grams (0.019 mole) of aniline was substitutedfor the1.70 grams of cyclohexanoneoxime. The yield was 6.0 grams of product,m.p. 8890C.

EXAMPLE 6 H c n,

O 3 n \NHNHJZOCH,

The procedure of Example 4 was repeated in its entirety except 1.37grams (0.015 mole) of methylhydrazinocarboxylate was substituted for the1.70 grams of cyclohexanoneoxime and only a 24 hour reaction period wasused instead of 2 days. The yield was 5.0

grams of product, m.p. 83-86C.

EXAMPLE 7 EXAMPLES a C. nSP Z 5 O 3 NHCH The procedure of Example 7 wasrepeated in its entirety except 1.1 grams of methylamine gas wassubstituted for the n-butylamine. The product yield was 3.8 grams, m.p.81-83C.

Other compounds were made in a similar manner using appropriate startingmaterials. The compounds are listed in Table l.-

TABLE I Example 9 3 \NHCHZCH2CH3 Example 10 Example 1 l Example 12 CHCH=CH Example 1 3 Example 14 Example 16 \NHCHZCHQOH 4. Two-spotted Mite(2-SM) Tetranychus urticae (Koch) 5. Salt-Marsh Caterpillar (SMC)Estigmene acrea (Dr m 6. Beet armyworm (BAW) Spodoptera e'xigua (Hubner)7. Tobacco budworm (TBW) Heliothis virescens (Fabricius) Aliquots of thetoxicants, dissolved in an appropriate solvent, are diluted in watercontaining 0.018% of a wetting agent, Sponto 221 (a polyoxyether ofalkylated phenols blended with organic sulfonates). Test concentrationsrange from 0.1% downward to that at which 50% mortality is obtained. Inthe tests, for these species, ten 1-month old nymphs of the Lygus Bugare placed in a circular cardboard cage sealed on one end withcellophane and covered by a cloth netting on the other. Testconcentrations for the Lygus Bug ranged from 0.05% downward to that atwhich 50% mortality was obtained. Each of the aqueous suspensions of thecandidate compounds are sprayed onto the insects through the clothnetting by means of a hand spray gun. Per cent mortality in each case isrecorded after 72 hours, and the LD value expressed as per cent oftoxicant in the aqueous spray is recorded. The results are in Table IIunder Column LB.

The following procedure is used to test houseflies: A stock solutioncontaining 0.1 .per cent by weight of the toxicant in an appropriatesolvent is prepared. Aliquots of this solution are combined with 1milliliter of an acetone-peanut oil solution in a 60 mm'oD. aluminum panand allowed to dry. The aliquots are selected to achieve desiredtoxicant concentration ranging from 100 pg per aluminum pan to that atwhich 50% mortality was attained. The aluminum pans are placed in acircular cardboard cage, closed on the bottom with cellophane andcovered on top with cloth netting. Twentyfive female houseflies areintroduced into the cage and g, the per cent mortality is recorded after48 hours. The LD values are expressed in terms of p. per 25 femaleflies. LD values obtained in the above-mentioned housefly test are.found in Table II under Column HF. The compound is dissolved in theappropriate solvent and dilutedto a concentration of 0.1 per cent withwater containing 0.018% Sponto 221. A portion of the leaf from a bitterdock (Rumex obtusifolius) plant is immersed in the test solution forseconds and allowed 10 to.clry. When dry, the leaf is placed in a Petridish containing a 9 cm disc of moistened filter paper. Five 3rdinstarsaltmars h caterpillar larvae are placed on the treated leaf. Mortalityis recorded after 72 hours. Test concentrations range from 0.1 per centto that at which 50% mortality is obtained. This latter concentration isrecorded as the LD value for the test compound.

The test method for the cotton bollworm, beet armyworm and tobaccobudworm is identical to the above except that Romaine lettuce (Lactucasaliva) is used as 0 the test plant rather than bitter clock.

The compounds are also active against two-spotted mite (2-SM)Tetranychus urticae (Koch). Pinto bean plants (Phaseolus sp.) areutilized as the host plant and infested with 50 to 75 mites of variousages. Twentyfour hours after infestation, they are sprayed to the pointof run off with aqueous suspension of the toxicant. Test concentrationsrange from 0.05% to that at which 50%-mortality is obtained. The valuesobtained in test are found in Table II under the Columns TABLE IIExample 2-SM No. HF LB BA PE Eggs SMC BAW TBW The compounds of thisinvention are generally embodied into a form suitable for convenientapplication. For example, the compounds can be embodied into pesticidalcompositions which are provided in the form of emulsions, suspensions,solutions, dusts and aerosol sprays. In general, such compositions willcontain, in addition to the active compound, the adjuvants which arefound normally in pesticide preparations. In these compositions, theactive compounds of this invention can be employed as the sole pesticidecomponent or they can be used in admixture with other compounds havingsimilar utility. The pesticide compositions of this invention cancontain, as adjuvants, organic solvents, such as sesame oil, xylenerange solvents, heavy petroleum, etc.; water; emulsifying agents;surface active agents; talc; pyrophyllite; diatomite; gypsum; clays;propellants, such as dichlorodifluoromethane, etc. If desired, however,the active compounds can be applied directly to feedstuffs, seeds, etc.upon which the pests feed. When applied in such a manner, it will beadvantageous to use a compound which is not volatile. In connection withthe activity of the presently disclosed pesticidal compounds, it shouldbe fully understood that it is not necessary that they be active assuch. The purposes of this invention will be fully served if thecompound is rendered active by external influences, such as light or bysome physiological action which occurs when the compound is ingestedinto the body of the pest.

The precise manner in which the pesticidal compositions of thisinvention are used in any particular instance will be readily apparentto a person skilled in the art. Generally, the active pesticide compoundwill be embodied in the form of a liquid composition; for example, anemulsion, suspension, or aerosol spray. While the concentration of theactive pesticide in the present compositions can vary within rather widelimits, ordinarily thepesticide compound will comprise not more thanabout 50.0% by weight of the composition. Preferably, however, thepesticide compositions of this invention will be in the form of spraytank solutions or suspensions containingabout 0.1 to 1.0% by weight ofthe active pesticide compound.

What is claimed is:

1. The method which comprises killing insects and mites by contactingthem with an insecticidally and miticidally effective amount of acompound of the formula CHt-Cf cu kart-cf wherein R is lower alkylhaving 1 to 4 carbon atoms, and R is C,H, \C2H5 5. The method as setforth in claim 1 wherein R is C H and R is 6. The method as set forth inclaim 1 wherein R is C2H5 and R2 18 7. The method as set forth in claim1 wherein R is 8. The method as set forth in claim 1 wherein R is CgHsand R2 iS NHCH2CH2CH3;

9. The method as set forth in claim 1 wherein R is C2H5 and R2 iS 10.The method as set forth in claim 1 wherein R is C2H5 and R2 is 11. Themethod as set forth in claim 1 wherein R is C2H5 and R2 is 12. Themethod as set forth in claim 1 wherein R is C H and R is NHCH 13. Themethod as set forth in claim 1 wherein R is C2H5 and R2 is 14. Themethod as set forth in claim 1 wherein R is C 11 and R is 15. The methodas set forth in claim 1 wherein R is C H and R is 16. The method as setforth in claim 1 wherein R is C H and R is 17. The method as set forthin claim 1 wherein R is C l-l and R is 18. The method as set forth inclaim 1 wherein R is C l-l and R is SO NH 19. The method as set forth inclaim 1 wherein R is C2H5 and R2 iS 20. The method as set forth in claim1 wherein R is C H and R is 21. The method as set forth in claim 1wherein R is C H and R is 22. The method as set forth in claim 1 whereinR is C H and R is C2H5 and R2 is 24. The method as set forth in claim 1wherein R is c n and R is crncrncm N s CH3 2 25. The method as set forthin claim 1 wherein R is C H and R is 26. The method as set forth inclaim 1 wherein R is C2H5 and R2 iS UNITED STATES PATENT OFFICECERTIFICATE OF CORRECTION PATENT NO. 3,917,827

DATED November 4, 1975 INVENTOR(S) Don R. Baker It is certified thaterror appears in the above-tdentified patent and that said LettersPatent are hereby corrected as shown below:

Column 6, Table 1, Example 34 should read as follows:

Column 8, Table II, under the heading "SMC" for Example No. 6, the entryshould read .l

Column 12, the formula in Claim 24 should read:

--- N JH--CH CI-l Signed and Scaled this Eighth Day of March 1977 [SEAL]Arrest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer (vmmissr'rmer ofParenrsand Trademarks

1. THE METHOD WHICH COMPRISES KILLING INSECTS AND MITES BY CONTACTINGTHEM WITH AN INSECTICIDALLY AND MITICIDALLY EFFECTIVE AMOUNT OF ACOMPOUND OF THE FORMULA
 2. The method as set forth in claim 1 wherein R1is C2H5 and R2 is NH(CH2)11CH3.
 3. The method as set forth in claim 1wherein R1 is C2H5 and R2 is NHCH2CH2OCH3.
 4. The method as set forth inclaim 1 wherein R1 is C2H5 and R2 is
 5. The method as set forth in claim1 wherein R1 is C2H5and R2 is
 6. The method as set forth in claim 1wherein R1 is C2H5 and R2 is NHCH2CH2CH2CH3.
 7. The method as set forthin claim 1 wherein R1 is C2H5 and R2 is NHCH3.
 8. The method as setforth in claim 1 wherein R1 is C2H5 and R2 is NHCH2CH2CH3.
 9. The methodas set forth in claim 1 wherein R1 is C2H5 and R2 is
 10. The method asset forth in claim 1 wherein R1 is C2H5 and R2 is
 11. The method as setforth in claim 1 wherein R1 is C2H5 and R2 is
 12. The method as setforth in claim 1 wherein R1 is C2H5 and R2 is
 13. The method as setforth in claim 1 wherein R1 is C2H5 and R2 is NHCH2CH2OH.
 14. The methodas set forth in claim 1 wherein R1 is C2H5 and R2 is
 15. The method asset forth in claim 1 wherein R1 is C2H5 and R2 is
 16. The method as setforth in claim 1 wherein R1 is C2H5 and R2 is
 17. The method as setforth in claim 1 wherein R1 is C2H5 and R2 is
 18. The method as setforth in claim 1 wherein R1 is C2H5 and R2 is
 19. The method as setforth in claim 1 wherein R1 is C2H5 and R2 is NHCH2CH2CH2OH.
 20. Themethod as set forth in claim 1 wherein R1 is C2H5 and R2 is
 21. Themethod as set forth in claim 1 wherein R1 iS C2H5 and R2 is
 22. Themethod as set forth in claim 1 wherein R1 is C2H5 and R2 is
 23. Themethod as set forth in claim 1 wherein R1 is C2H5 and R2 is
 24. Themethod as set forth in claim 1 wherein R1 is C2H5 and R2 is
 25. Themethod as set forth in claim 1 wherein R1 is C2H5 and R2 is
 26. Themethod as set forth in claim 1 wherein R1 is C2H5 and R2 is NHCH2CH CH2.